CN101244826A - Method for producing silicon dioxide silica aerogel by drying in atmosphere pressure with rice hull as raw material - Google Patents
Method for producing silicon dioxide silica aerogel by drying in atmosphere pressure with rice hull as raw material Download PDFInfo
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- CN101244826A CN101244826A CNA2008100612017A CN200810061201A CN101244826A CN 101244826 A CN101244826 A CN 101244826A CN A2008100612017 A CNA2008100612017 A CN A2008100612017A CN 200810061201 A CN200810061201 A CN 200810061201A CN 101244826 A CN101244826 A CN 101244826A
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- Prior art keywords
- silane
- acid
- rice husk
- hydrogel
- methyl
- Prior art date
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Links
- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 57
- 235000009566 rice Nutrition 0.000 title claims abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 title claims abstract description 12
- 238000001035 drying Methods 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 3
- 240000007594 Oryza sativa Species 0.000 title 1
- 239000004965 Silica aerogel Substances 0.000 title 1
- 241000209094 Oryza Species 0.000 claims abstract description 56
- 239000010903 husk Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000000499 gel Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000017 hydrogel Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 27
- -1 trimethylsiloxy group methyl-monosilanes Chemical class 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 8
- XDIWYXGVXYCUSV-UHFFFAOYSA-N 2-methylpropylsilicon Chemical compound CC(C)C[Si] XDIWYXGVXYCUSV-UHFFFAOYSA-N 0.000 claims description 7
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 claims description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 2
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 claims description 2
- PXJZCBUXFVZSLL-UHFFFAOYSA-N CO[SiH2]OC.C=CC Chemical compound CO[SiH2]OC.C=CC PXJZCBUXFVZSLL-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 2
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 claims description 2
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000012629 purifying agent Substances 0.000 claims 2
- 239000004964 aerogel Substances 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 13
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000000352 supercritical drying Methods 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 210000000056 organ Anatomy 0.000 abstract 1
- 231100000167 toxic agent Toxicity 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 239000012153 distilled water Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002154 agricultural waste Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000012895 Gastric disease Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 208000018556 stomach disease Diseases 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention discloses a drying preparation method of silicon dioxide aerogel under atmospheric pressure by using rice husk as raw material, which comprises the following procedures: (1) preparation of rice husk sol; (2) aging of gel; (3) solvent exchange; (4) surface modification of gel; (5) drying under atmospheric pressure. Instead of expensive toxicant organ silicon source, agricultural trashes rice husk is used as raw material, thus greatly reduce the cost; instead of super-critical drying, drying under atmospheric pressure greatly reduces the requirements for the whole process on the equipment, greatly improves the safety performance on one hand, also greatly reduces the running cost on the other. The method in the invention has the advantages of simple technology, easy operation, which is suitable for scale production.
Description
Technical field
The present invention relates to the chemical materials preparation field, relate in particular to a kind of preparation method of aerosil.
Background technology
Rice husk is large agricultural waste, annual about 200,000,000 tons of the paddy of producing per year of China, and wherein the rice husk quality accounts for 20%.Because the rice hull cellulose tissue is covered with hard silicic acid thing, nutritive value is extremely low, and digestible nutrient is negative value, and easily causes the animal intestine gastropathy.Because xylogen and siliceous content height, so rice husk is difficult for suction, and directly being applied to the field, to make fertilizer not perishable.This characteristic limitations its development and use.Now, have only the minute quantity rice husk to obtain utilization, built up the power station of annual electricity generating capacity 5000000 kWh as the Wusuli River, Wenzhou rice industry company limited in 06 year.A large amount of rice husks in the rural area or grain rice source mill pile up like a mountain, become reluctant waste, both contaminate environment caused fire again easily, had become society's one big public hazards.
Amorphous Si O
2Be one of main component of rice husk, account for 18.8%-22.3%, in rice husk, be mesh structural porous structure.Therefore, exist the organic constituent of removing rice husk in theory, the structural framework of in store silicon, thus make the nanometer SiO of high absorbability, high specific area
2Possibility.As far back as 1986, China just someone applied for a patent CN86107192, produced white carbon black, product SiO by the low-temperature bake rice husk
2Content reaches 98%, and specific surface area is at 60-150m
2/ g.To at present, existing many patents and document have proposed to produce nanometer SiO by burning or carbonization rice husk
2Method.
The described method of CN1202993C is utilized the mineral acid treatment rice husk, and making particle diameter through steps such as washing, drying, burning, pulverizing again is 30-80nm, the nanometer SiO of purity 98.0-99.9%
2CN1234605C makes long-chain organic compound cracking in the rice husk by the solution that contains the oxidisability solute, and heated oxide is removed organic compound then, again water, acidic solution or other solution rinsing residue SiO
2To remove trace impurity, produce fine, white, high purity amorphous Si O
2In patents such as CN1116128C, CN1039898C, also disclose respectively and utilized rice hull ash to produce amorphous porous SiO
2Method.The relative extraction SiO of ore in the past
2, make raw material with rice husk and extract SiO
2Production technique is simple, has exempted complicated removal of impurities operation, and production process is easy to control, and cost is low, and is environmentally friendly, improved the utilization ratio of rice husk greatly.
With respect to common SiO
2Powder, SiO
2Aerogel is as a kind of novel low density, high porosity nano-porous materials of controllable structure, (typical bore hole size is 1-100nm because of its successive network structure, nanometer scale bore hole size and particle diameter, network structure elements is of a size of 1-20nm, hole ratio is up to 80.0%-99.8%, and specific surface area is up to 800-1000m
2/ g) have mechanics, acoustics, calorifics, an optical property that obviously is different from corresponding macroscopical vitreous material, as extremely low solid-state and gaseous state thermal conductivity, low-refraction, low elastic modulus, low acoustic impedance, strong absorption property etc., have a wide range of applications in fields such as aerospace, chemical industry, energy saving building, military affairs, communication, electronics, metallurgy, caused numerous investigators' great interest as the novel material of 21 century.
The most common SiO
2Aerogel is a raw material with methyl silicate (TMOS), tetraethoxy (TEOS), multi-polysiloxane (E-40), poly-diethoxy siloxanes organic silicides such as (PDEOS) mostly, and combining with supercritical drying or constant pressure and dry technology by sol-gel technique makes.But organic silication price lattice height is unfavorable for commercially producing.For reducing cost, some investigators turned to rice husk to burn sight or carbonization after rice hull ash on.
With the rice hull ash is feedstock production SiO
2The method of aerogel, all adopt Supercritical Drying Technology as patent CN1222473C, CN1317188C, need to adopt high pressure vessel, and the temperature and pressure during to drying carries out strictness control, still there are problems such as energy consumption is big, operating process is complicated, drying cycle is long, running cost is high, poor safety performance, are not suitable for producing in enormous quantities.
For overcoming this shortcoming, publication number is to disclose a kind of rice hull ash of utilizing in the patent documentation of CN1278933C to be raw material, and constant pressure and dry prepares SiO
2The method of aerogel adopts the positive silicon ester of silicoorganic compound [Si (OR)
4] or alkyl silicate [R
4-nSi (OR)
n] be the hydrophobic surface modifier, in the 0-15min that the water-sol forms, add silicoorganic compound, form hydrogel, hydrogel is prepared specific surface area 400-800m through aging, washing, the laggard capable constant pressure and dry of organic solvent displacement moisture
2/ g, pore volume 1.0-4.0cm
3/ g, apparent density 0.1-0.5g/cm
3SiO
2Aerogel.Because SiO
2The forming process of gel is Si (OH)
4In the process of the continuous crosslinking polymerization of hydroxyl-OH, its degree of crosslinking has determined SiO
2Therefore the integrity of gel network structure has also determined SiO
2Factors such as the apparent density of aerogel, specific surface area, porosity, pore volume.And SiO
2The process of the surface-hydrophobicized processing of aerogel also is-process that OH is replaced by hydrophobic grouping the too early positive silicon ester of adding silicoorganic compound [Si (OR)
4] or alkyl silicate [R
4-nSi (OR)
n], can make Si (OH)
4In hydroxyl-OH colloidal sol crosslinking polymerization become and just replaced before the gel by hydrophobic grouping, therefore be difficult to form complete gel network structure, cause the aerogel apparent density height prepared with this method, specific surface area is little.In addition, the positive silicon ester of silicoorganic compound [Si (OR)
4] or alkyl silicate [R
4-nSi (OR)
n] comparatively violent with the water reaction, therefore add and certainly will cause silicoorganic compound waste, SiO at sol phase
2The aerogel production cost increases, and hydroxyl-OH is difficult to be replaced by hydrophobic grouping fully, and unavoidably there is the wetting ability problem in product, is easy to absorb moisture and causes degradation even structure to cave in product rejection in the process of depositing, transporting.
In addition, the burning of rice husk and carbonization are processes more rambunctious.Temperature is crossed to hang down and may be caused carbonization incomplete, influences the purity of product; High slightly or time of temperature is long slightly all might to make a large amount of ash, carbonaceous residue or metallic residue remain in SiO
2In the hole of mesh structural porous structure, the SiO of extraction
2High-content only can reach about 98%, can only be used for some to the not high Industrial products of purity requirement and material of construction etc.; Improve temperature and oxidation of impurities but can not be able to be guaranteed SiO
2Form can't help amorphous state and change crystal form into and lose absorption property, destroy porous network structure.In addition, the process of burning itself is exactly the process of a thermal waste, also is difficult in the burning process avoid discharging environmentally harmful gas or flue dust, causes environmental pollution, harm humans health.
Summary of the invention
The invention provides a kind of technology environmental protection, simple, the method for preparing aerosil that cost is low.
A kind of method for preparing aerosil with the rice husk for the raw material constant pressure and dry may further comprise the steps:
(1) rice husk water-sol preparation
Rice husk and concentration are mixed alkaline solution and rice husk weight ratio 1-200 for the 0.1-15.0mol/L alkaline solution: 1, at 30-260 minute after-filtration of temperature 20-150 ℃ of leaching, filtrate transfers pH value to 4-12 with acid, obtains the water-sol.
The preferred 1-12mol/L of alkaline concentration, alkaline solution and the preferred 2-50 of rice husk weight ratio: 1, the preferred 30-180 of leaching time minute, preferred 4.5-11.5 when filtrate is transferred pH value with acid.
(2) gel is aging
The water-sol is 5-90 ℃ in temperature and left standstill 5 minutes-72 hours, forms hydrogel, and hydrogel is 10-90 ℃ of aging 0-50 hour in temperature.
The water-sol leaves standstill and all preferred 10-70 ℃ of hydrogel aged temperature, all preferred 0.5-48 hour time.
(3) solvent exchange
The ionized water that contains in the hydrogel after will wearing out with solvent cements out, 15-95 ℃ of displacement temperature, time 0.5-480 hour.
Solvent with aging after the volume ratio of hydrogel be 0.1-100: 1, preferred 1-50: 1.
The preferred 15-80 of the temperature of solvent exchange ℃, the preferred 1-360 of time swap hour, the displacement number of times was 1-50 time, preferred 1-30 time.
The metathetical mode can be one or more in usefulness solvent washing, backflow, the immersion.Can select a kind of solvent to replace as required, or select several different solvents to replace successively.
(4) gel surface is modified
To mix with silicoorganic compound through the hydrogel behind the solvent exchange, and carry out surface hydrophobicity at temperature 10-95 ℃ and modified 1-240 hour, wherein the volume ratio of silicoorganic compound and hydrogel is 0.1-20: 1.
Carry out that gel surface is modified the preferred 15-80 of temperature ℃, preferred 10-120 of time hour, the preferred 0.1-10 of the volume ratio of silicoorganic compound and hydrogel: 1
The mode that silicoorganic compound carry out the gel surface modification can be to soak, but is not limited to soak.Silicoorganic compound can use separately, also can use with solvent described in the step (3), and the blended ratio is 0.001-50: 1, and preferred 0.1-10: 1, the solvent that adopts when the solvent of specifically selecting for use is not limited to implementation step (3).
(5) constant pressure and dry
The hydrogel that to modify through surface hydrophobicity is 20-380 ℃ of constant pressure and dry 0.5-300 hour in temperature, can make low density high hydrophobicity SiO
2Aerogel.
The preferred 40-240 of drying temperature ℃, preferred 1-40 of time hour.
Alkali is NaOH, KOH, NH in the described alkaline solution of step (1)
4OH, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3In one or more, solvent is water and/or alcohol.
For enhancing product performance and production efficiency, can be optimized step (1): at the described rice husk of step (1) with before alkaline solution mixes, earlier it is carried out purification process, on the one hand the hydrocarbon molecule grown in the organism of one of rice husk main component such as xylogen and Mierocrystalline cellulose are cut into lower carbon number hydrocarbons molecule short, that can be eliminated with acid and/or oxygenant; Remove impurity metal ion such as iron, magnesium, calcium etc. on the other hand, avoid its remnants in the product aerogel,, obtain having bigger serface more, less dense, SiO that transparency is higher to improve process efficiency
2Aerogel can guarantee that rice husk carries out subsequent reactions under the condition that does not need to burn simultaneously, has reduced pollution, makes technology environmental protection more.
Wherein, described acid can be HF, HCl, H
2SO
4, H
3PO
4, HNO
3, H
2CO
3, HClO
3In one or more; Described oxygenant can be superoxide such as H
2O
2Or in the peroxyacetic acid, permanganate, concentrated nitric acid, the vitriol oil, perchlorate one or more.
Described acid and/or oxygenant can mix according to the difference of its kind and use, or successively use.Acid and/or oxidant concentration are 0.1-15.0mol/L, preferred 1-12.0mol/L, and acid and/or oxygenant and rice husk weight ratio 1-200: 1, preferred 1-50: 1.
Acid and/or oxygenant and rice husk blended mode can be that rice husk joins in acid and/or the oxygenant, also can be that acid and/or oxygenant join in the rice husk.
The acid that step (1) is used to regulate the pH value is mineral acid and/or organic acid, and mineral acid can be HF, HCl, H
2SO
4, H
3PO
4, HNO
3, H
2CO
3Or HClO
3In one or more; Organic acid contains acidic-group carboxyl-COOH and/or sulfonic acid-SO for one or more
3The acid organism of H.The blended mode can be that acid is added drop-wise in the filtrate, also can be that filtrate is added drop-wise in the acid.The HF that preferred acidic is stronger, HCl, H
2SO
4, HNO
3, oxalic acid, acetic acid, citric acid or contain at least a in the strong-acid ion exchange resin of sulfonic acid group.。When adopting sour beyond the acidic ion exchange resin, the concentration of acid is 0.1-8mol/L, preferred 1-5mol/L.When adopting acidic ion exchange resin, need resin is separated from colloidal sol.
Solvent described in the step (3) is water, alcohol, ketone, aromatic hydrocarbon, low-carbon alkanes.Wherein water can be ortho-water, distilled water, deionized water; Alcohol can adopt methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol; Ketone can be acetone or butanone; Aromatic hydrocarbon can be benzene,toluene,xylene, ethylbenzene, propyl benzene or isopropyl benzene; Low-carbon alkanes can be that (structure is C to carbonatoms 1～16
nH
2n+2(n=1-16)) liquid alkane.The preferably not toxic water of tool, alcohol, liquid low-carbon alkanes substantially.Preferred alcohol does not comprise methyl alcohol.
Silicoorganic compound are methyltrimethoxy silane described in the step (4), dimethyldimethoxysil,ne, the trimethylammonium methoxy silane, tetraethoxysilane, Union carbide A-162, dimethyldiethoxysilane, trimethylethoxysilane, ethyl trimethoxy silane, diethyl dimethoxy silane, the triethyl methoxy silane, triethyl-ethoxy-silicane alkane, the diethyl diethoxy silane, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, methyl ethylene dimethoxy silane, vinyl trichloro silane, hexamethyldisiloxane, hexamethyldisilazane, seven methyl sily oxide, heptamethyldisilazane, chloropropyl triethoxysilane, chloropropylmethyldimethoxysilane, two (2-methyl-propyl) silane of dimethoxy, two trimethylsiloxy group methyl-monosilanes, two (1, the 2-methyl dichloro is silica-based) ethane, two (1, the 2-trichlorine is silica-based) ethane, two (1,2-methyl dimethoxy oxygen base is silica-based) ethane, two (1,2-methyl diethoxy is silica-based) ethane, two (1, the 2-trimethoxy is silica-based) ethane, two (1, the 2-triethoxy is silica-based) ethane, octyltri-ethoxysilane, trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, chlorotriethyl silane, in diethyl dichlorosilane or the ethyl trichlorosilane one or more.
Two (2-methyl-propyl) silane of preferred dimethoxy or two trimethylsiloxy group methyl-monosilane.Select suitable silicoorganic compound, during especially above-mentioned preferred silicoorganic compound, can obtain the better SiO of hydrophobic performance
2Aerogel.
Method of the present invention is raw material for directly utilizing cheap, resourceful rice husk, has realized the preparation of low density high hydrophobicity aerogel under the condition of constant pressure and dry.Compared with prior art have following advantage:
(1) technology simple, be convenient to operation, be suitable for large-scale production.This is invented used technology and directly utilizes rice husk to be raw material, has avoided unmanageable rice husk to burn or carbonization process; Utilize the constant pressure and dry technology, avoided the supercritical process of complicated operation, so whole process flow compares with existing technology, obviously more simple and convenient.
(2) cost is low; The present invention is a raw material with the agricultural waste rice husk, replaces costing an arm and a leg, have certain toxic organosilicon source, and cost is reduced greatly; Constant pressure and dry replaces supercritical drying, on the one hand whole technology is reduced greatly to the requirement of equipment, and safety performance promotes greatly, and running cost is greatly descended.
(3) Si (OH) in colloidal sol
4Hydroxyl-OH cross-linking polymerization comparatively abundant, the gel phase that network structure is comparatively complete is carried out finishing, can guarantee product SiO
2The porosity of aerogel, pore size distribution state are even more ideal, therefore obtain the SiO that density is low, porosity is high
2The aerogel product also can be avoided the waste of coating materials simultaneously.Adopt new coating materials, can make SiO
2The hydrophobicity of aerogel improves.
(4) than the similar technology that has now in patent or the document, product SiO
2Aerogel density is lower, hydrophobicity is stronger, overcome fully deposit, deficiency that transportation causes degradation even structure to be caved in because of suction, every performance is all very near the SiO of Supercritical Drying Technology preparation
2Aerogel.After testing, product density is low to moderate 0.04-0.08g/cm
3, specific surface area 400-900m
2/ g, porosity is higher than 99%, and contained aperture is a nano level, pore size distribution range 1-50nm, mean pore size 10-20nm.
(5) utilize agricultural waste, environmentally friendly.
Embodiment
Embodiment 1
The NaOH aqueous solution of 100 gram rice husks and 5.0L0.1mol/L and under high pressure 150 ℃ react 60min, it is 10.0 that the filtrate that obtains after the filtration is neutralized to the pH value with the sulfuric acid of 2mol/L with it; At room temperature leave standstill after 5 minutes and obtain hydrogel.The hydrogel of gained was at room temperature worn out 30 hours, and successively with the ionized water that contains in distilled water, the ethanol replacing water gel, the volume ratio of solvent and gel is a gel: distilled water: ethanol=1: 50: 5, the time was respectively 360 hours, 20 hours.Soak gel with two (2-methyl-propyl) silane of dimethoxy again under 40 ℃ of temperature, the volume ratio of two (2-methyl-propyl) silane of dimethoxy and gel is 2: 1, and the time is 10 hours.Be placed on after the taking-up in 40 ℃ the baking oven dry 20 hours, and promptly made white translucent aerosil.After testing, its apparent density is 0.082g/cm
3, specific surface area is 442m
2/ g, transparence 76.8%.Carry out hydrophobicity and measure, product is placed directly on the water surface, weigh after 20 days, weightening finish 7.0%.
Embodiment 2
100 gram rice husks mix with the NaOH spirituous solution of 100ml1mol/L, and are heated to 60 ℃ react 120min under normal pressure, and it is to leave standstill under 12.0,15 ℃ to obtain hydrogel in 48 hours that the filtrate that obtains after the filtration is neutralized to the pH value with the hydrochloric acid of 1mol/L with it.The hydrogel of gained 15 ℃ aging 48 hours down, with containing ionized water 3 times in the ethanol replacing water gel, every 24 hours 1 time, the volume ratio of ethanol and hydrogel is 10: 1.With two (2-methyl-propyl) silane of dimethoxy hydrogel is carried out finishing down at 30 ℃ again, the volume ratio of two (2-methyl-propyl) silane of hydrogel and dimethoxy is 1: 3, and the time is 48 hours.In being placed on 25 ℃ baking oven dry 240 hours, promptly make white translucent aerosil.After testing, its apparent density is 0.074g/cm
3, specific surface area is 481m
2/ g, transparence 79.5%.Carry out hydrophobicity and measure, product is placed directly on the water surface, weigh after 20 days, weightening finish 6.7%.
Embodiment 3
200 gram rice husk and the KOH aqueous solution of 2L0.9mol/L and the 90min that under normal pressure, seethe with excitement, it is 6.5 that the filtrate that obtains after the filtration is neutralized to the pH value with acidic cation-exchange resin with it, filtration is once more left standstill under 50 ℃ and was obtained hydrogel in 30 minutes.The hydrogel of gained wore out 12 hours down at 50 ℃, use distilled water immersion gel 5 hours in 80 ℃ of thermostat water baths, the volume ratio of distilled water consumption and gel is 50: 1, soaks gel with normal heptane then, the volume ratio of normal heptane and gel 10: 1, the time is 1 hour.Use the mixed liquid dipping gel of two trimethylsiloxy group methyl-monosilanes and normal heptane again, the volume ratio of two trimethylsiloxy group methyl-monosilanes, normal heptane, gel is 1: 3: 1, and the time is 30 minutes.Be placed in 180 ℃ the baking oven dry 2 hours, and promptly made white translucent aerosil.After testing, its apparent density is 0.054g/cm
3, specific surface area is 583m
2/ g, transparence 87.1%.Carry out hydrophobicity and measure, product is placed directly on the water surface, weigh after 20 days, weightening finish 6.9%.
Embodiment 4
The H of 300 gram rice husks and 300ml12.0mol/L
2O
2Mix, react 60min down, filter at 50 ℃.The NaCO of filtrate and 1.2L1.5mol/L
3Aqueous solution, and at 80 ℃ of following reaction 30min, it is to leave standstill under 4.5,80 ℃ to obtain hydrogel in 90 minutes that the filtrate that obtains after the filtration is neutralized to the pH value with the acetic acid of 5mol/L with it.The hydrogel of gained wore out 30 minutes down at 90 ℃.Cool the temperature to 25 ℃, successively with the ionized water that contains in ethanol, the normal heptane replacing water gel, the volume ratio of solvent and gel is a gel: ethanol: normal heptane=1: 10: 1, the time was respectively 72 hours, 36 hours.With two trimethylsiloxy group methyl-monosilanes gel is carried out surface hydrophobicity down at 25 ℃ again and modify, the volume ratio of two trimethylsiloxy group methyl-monosilanes and gel is 1: 2, and the time is 20 hours.Be placed in 240 ℃ the infrared drying oven dry 1 hour, and promptly made white translucent aerosil.After testing, its apparent density is 0.048g/cm
3, specific surface area is 597m
2/ g, transparence 93.7%.Carry out hydrophobicity and measure, product is placed directly on the water surface, weigh after 20 days, weightening finish 5.7%.
Embodiment 5
The H of 500 gram rice husks and 1.5L10mol/L
2SO
4Mix, at room temperature reacted 60 minutes, after the filtration, filtrate and 2L5mol/L, temperature is 90 ℃ NaOH aqueous solution and reacts 20min under 90 ℃.The filtrate that obtains after the filtration is used the HNO of 0.1mol/L
3It is neutralized to the pH value is to leave standstill under 11.0,70 ℃ to obtain hydrogel in 60 minutes.The hydrogel of gained wore out 2 hours down at 70 ℃, cool the temperature to 40 ℃, successively with the ionized water that contains in distilled water, the acetone replacing water gel, the volume ratio of solvent and gel is a gel: distilled water: acetone=1: 20: 2, the time was respectively 48 hours, 10 hours.At room temperature use the mixed solution of two trimethylsiloxy group methyl-monosilanes and acetone that gel is carried out the surface hydrophobicity modification again, the volume ratio of two trimethylsiloxy group methyl-monosilanes, acetone and gel is 1: 10: 1, and the time is 1 hour.Be placed in 120 ℃ the IR bake dry 3 hours, and promptly made white translucent aerosil.After testing, its apparent density is 0.053g/cm
3, specific surface area is 586m
2/ g, transparence 91.0%.Carry out hydrophobicity and measure, product is placed directly on the water surface, weigh after 20 days, weightening finish 6.4%.
Embodiment 6
The NH of 500 gram rice husks and 2L12mol/L
3OH mixes, and 30 ℃ are reacted 260min down.Filtrate that obtains after the filtration and the HNO of 0.5mol/L
3Mix, being neutralized to the pH value is to leave standstill under 4.0,10 ℃ to obtain hydrogel in 72 hours.At room temperature with two trimethylsiloxy group methyl-monosilanes and alcoholic acid mixed solution gel is carried out solvent exchange and surface hydrophobicity modification, the volume ratio of two trimethylsiloxy group methyl-monosilanes, ethanol and gel is 0.1: 10: 1, and the time is 60 hours.Be placed in 80 ℃ the baking oven dry 8 hours, and promptly made white translucent aerosil.After testing, its apparent density is 0.061g/cm
3, specific surface area is 520m
2/ g, transparence 84.9%.Carry out hydrophobicity and measure, product is placed directly on the water surface, weigh after 20 days, weightening finish 6.8%.
Claims (10)
1, a kind of method for preparing aerosil with the rice husk for the raw material constant pressure and dry may further comprise the steps:
(1) rice husk water-sol preparation
Rice husk and concentration are mixed for the 0.1-15.0mol/L alkaline solution, and at 30-260 minute after-filtration of temperature 20-150 ℃ of leaching, filtrate transfers pH value to 4-12 with acid, obtains the water-sol;
Alkali is NaOH, KOH, NH in the described alkaline solution
4OH, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3In one or more, solvent is water and/or alcohol;
(2) gel is aging
The water-sol is 5-90 ℃ in temperature and left standstill 5 minutes-72 hours, forms hydrogel, hydrogel temperature 10-90 ℃ aging 0-50 hour;
(3) solvent exchange
Contain ionized water, 15-95 ℃ of displacement temperature, time 0.5-480 hour in the hydrogel after going out to wear out with solvent exchange;
(4) gel surface is modified
To mix with silicoorganic compound through the hydrogel of solvent exchange, carry out surface hydrophobicity at temperature 10-95 ℃ and modified 1-240 hour, wherein the volume ratio of silicoorganic compound and hydrogel is 0.1-20: 1;
(5) constant pressure and dry
The hydrogel that to modify through surface hydrophobicity obtained aerosil at 20-380 ℃ of constant pressure and dry 0.5-300 hour.
2, the method for claim 1 is characterized in that: the described purifying agent concentration of step (1) 1-12mol/L, leaching time 30-180 minute, filtrate transferred pH value to 4.5-11.5 with acid.
3, the method for claim 1 is characterized in that: described purifying agent of step (1) and rice husk weight ratio 1-200: 1.
4, the method for claim 1 is characterized in that: the described rice husk of step (1) with before alkaline solution mixes with acid and/or oxygenant purification process;
Described acid is HF, HCl, H
2SO
4, H
3PO
4, HNO
3, H
2CO
3Or HClO
3In one or more;
Described oxygenant is H
2O
2, in peroxyacetic acid, permanganate, concentrated nitric acid, the vitriol oil or the perchlorate one or more;
Described acid or oxidant concentration are 0.1-15.0mol/L, acid or oxygenant and rice husk weight ratio 1-200: 1.
5, method as claimed in claim 4 is characterized in that: described acid or oxidant concentration are 1-12.0mol/L, and acid or oxygenant and rice husk weight ratio are 1-50: 1.
6, the method for claim 1 is characterized in that: the water-sol leaves standstill with hydrogel aged temperature and is 10-70 ℃ in the step (2), and the time is 0.5-48 hour.
7, the method for claim 1 is characterized in that: in the step (3) temperature 15-80 ℃ of solvent exchange, time swap 1-360 hour, the displacement number of times was 1-30 time.
8, the method for claim 1 is characterized in that: carry out in the step (4) that gel surface is modified temperature 15-80 ℃, and time 10-120 hour, the volume ratio 0.1-10 of silicoorganic compound and hydrogel: 1.
9, the method for claim 1 is characterized in that: the solvent described in the step (3) is that water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, acetone, butanone, benzene,toluene,xylene, ethylbenzene, propyl benzene, isopropyl benzene or carbonatoms are one or more in 1～16 the liquid alkane.
10, the method of claim 1, it is characterized in that: silicoorganic compound are methyltrimethoxy silane described in the step (4), dimethyldimethoxysil,ne, the trimethylammonium methoxy silane, tetraethoxysilane, Union carbide A-162, dimethyldiethoxysilane, trimethylethoxysilane, ethyl trimethoxy silane, diethyl dimethoxy silane, the triethyl methoxy silane, triethyl-ethoxy-silicane alkane, the diethyl diethoxy silane, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, methyl ethylene dimethoxy silane, vinyl trichloro silane, hexamethyldisiloxane, hexamethyldisilazane, seven methyl sily oxide, heptamethyldisilazane, chloropropyl triethoxysilane, chloropropylmethyldimethoxysilane, two (2-methyl-propyl) silane of dimethoxy, two trimethylsiloxy group methyl-monosilanes, two (1, the 2-methyl dichloro is silica-based) ethane, two (1, the 2-trichlorine is silica-based) ethane, two (1,2-methyl dimethoxy oxygen base is silica-based) ethane, two (1,2-methyl diethoxy is silica-based) ethane, two (1, the 2-trimethoxy is silica-based) ethane, two (1, the 2-triethoxy is silica-based) ethane, octyltri-ethoxysilane, trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, chlorotriethyl silane, in diethyl dichlorosilane or the ethyl trichlorosilane one or more.
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